Azo compounds having a 2,4-dinitro-5-thiocyanophenyl diazo component radical

ABSTRACT

Compounds of the formula   &lt;IMAGE&gt;   wherein K is a coupling component radical, are useful for dyeing textile materials comprising a synthetic or semisynthetic, hydrophobic, high molecular weight material, e.g., linear aromatic polyesters, cellulose 21/2 acetate, cellulose triacetate and synthetic polyamides.

This application is a continuation-in-part of application Ser. No. 459,730, filed Jan. 20, 1983 and now abandoned.

The invention relates to rhodanphenylazo dyestuffs which, in particular, are useful for dyeing textile material.

The invention provides compounds of the formula ##STR2## in which K is a coupling component radical.

Preferably K is a disperse dye coupling component radical, more preferably of the aminobenzene series, unsubstituted or substituted or an N-heteocyclic fused ring system, unsubstituted or substituted. Typical groups by which both the aminobenzene series and N-heterocyclic fused ring system coupling radicals may be substituted are those shown attached to the phenyl coupling radical of the examples.

Most preferably K is K₁, where K₁ is a radical of formula II or of formula III ##STR3## in which R₁ is hydrogen, chloro, bromo, C₁₋₄ alkyl, C₁₋₄ alkoxy,

benzyloxy or --O--(CH₂)_(n) --A₁ --C₁₋₆ alkyl,

R₂ is hydrogen, chloro, bromo, C₁₋₂ alkyl, C₁₋₄ alkoxy, phenyl-(C₁₋₃ alkoxy), acyloxy or acylamino (e.g., --NHCO--(CH₂)_(n) --A₁ --C₁₋₆ alkyl,

R₃ and R₄ independently are selected from hydrogen; C₁₋₁₂ alkyl), C₃₋₄ alkenyl; C₃₋₄ alkynyl; benzyl; C₂₋₆ alkyl substituted by 1 or 2 substituents independently selected from hydroxy, C₁₋₄ -alkoxy, acyloxy, chloro, bromo, cyano, phenyl and phenoxy; and --(CH₂)_(n) --A₁ --C₁₋₆ alkyl,

A is C₃₋₇ alkylene or a group of the formula --O--C₂₋₄ alkylene-, with the proviso that the N-atom of the group of formula III is not attached to the oxygen atom,

each n independently is a number from 1-6, inclusive, and each A₁ independently is --O--, --O--CO--, --O--CO--O-- or --CO--O--.

In this specification, unless indicated to the contrary, those groups capable of being further substituted are not and any alkyl and alkylene groups present are linear or branched. Preferably any alkyl or alkoxy group present is methyl or ethyl or methoxy or ethoxy, respectively.

In this specification, where a symbol appears more than once in a formula its significances are independent of one another.

R₁, when C₁₋₄ alkoxyethoxy, is preferably 2-(C₁₋₄ alkoxy)ethoxy.

Throughout this specification, preferably any hydroxy, alkoxy, acyloxy, cyano, phenoxy or alkoxycarbonyl as a substituent on an alkyl group attached to an oxygen or nitrogen atom is other than in the 1-position and no carbon atom bears more than one such substituent.

Preferred acyl groups referred to in this specification are carbonyl or sulphonyl groups.

Preferably R₁ is R₁ ', where R₁ ' is hydrogen, C₁₋₂ alkoxy or --O--(CH₂)_(n) --A₁ --C₁₋₄ alkyl, more preferably the former two or 2-(C₁₋₂ alkoxy)-ethoxy.

Preferably R₂ is R₂ ', where R₂ ' is hydrogen, methyl, C₁₋₂ alkoxy, C₁₋₆ alkylcarbonylamino, (C₁₋₄ -alkoxy)carbonylamino, --NHCOCH₂ CH₂ Cl, --NHCO--CH═CH₂, --NHCO--CH═CH--CH₃ or --NHCO--(CH₂)_(n) --A₁ --C₁₋₆ alkyl, more preferably hydrogen, methyl, C₁₋₆ alkylcarbonylamino, (C₁₋₄ alkoxy)carbonylamino, --NHCO--CH═CH₂ or --NH--CO--CH═CH--CH₃.

Preferably each of R₃ and R₄ independently is selected from hydrogen; C₁₋₁₂ alkyl; C₃₋₄ alkenyl; C₂₋₆ alkyl substituted by one substituent selected from hydroxy, phenoxy, cyano and C₁₋₃ alkoxy; and --(CH₂)_(n) --A₁ --C₁₋₆ alkyl.

Preferably n is n', where n' is selected from 2-4, inclusive.

A preferred group of compounds of formula I are those in which

R₁ is hydrogen, R₂ is R₃ ', and each of R₃ and R₄ independently is C₁₋₆ alkyl or one of R₃ and R₄ is C₁₋₆ alkyl and the other is primary or secondary C₂₋₆ alkyl substituted other than in the 1-position by phenoxy.

Preferred acyloxy groups are selected from --O--CO--R₅, --O--CO--OR₅, --O--CO--NR₆ R₇, --O--SO₂ --R₅ and --O--SO₂ --NR₆ R₇ and preferred acylamino groups are selected from --NH--CO--R₅, --NH--CO--OR₅,

--NH--CO--NH₂, --NH--CO--NHR₅, --NH--CO--NR₆ R₇, --NH--SO₂ R₅, --NH--SO₂ --NR₆ R₇ and --NH--CO--(CH₂)_(n) --A,--C,--6 alkyl, wherein

each R₅ independently is selected from linear or branched C₁₋₆ alkyl, unsubstituted or substituted by one group selected from chloro, bromo, hydroxy, C₁₋₃ alkoxy and phenoxy; C₅₋₆ cycloalkyl; C₂₋₄ alkenyl, unsubstituted or substituted by chloro or bromo; phenyl, unsubstituted or substituted by 1 to 3 substituents independently selected from chloro, bromo, C₁₋₂ alkyl and C₁₋₂ alkoxy; and methyl or ethyl substituted by a phenyl group,

each R₆ and R₇ independently is C₁₋₄ alkyl, unsubstituted or substituted by one substituent selected from chloro, bromo, hydroxy and C₁₋₃ alkoxy; or phenyl, unsubstituted or substituted by 1 to 3 substituents independently selected from chloro, bromo, C₁₋₂ alkyl and C₁₋₂ alkoxy; or R₆ and R₇ together with the N-atom to which they are attached form a heterocyclic ring, preferably pyrrolidino, piperidino or morpholino.

Pages 1-3, 12 and 13 of parent application Ser. No. 459,730, filed Jan. 20, 1983, are hereby incorporated by reference as if they were set forth herein in their entirety.

Representative compounds of formula I are those wherein K is K_(1a), where K_(1a) is a group of formula IIa or IIIa ##STR4## in which

R_(1a) is hydrogen, chloro, bromo, C₁₋₄ alkyl, C₁₋₄ -alkoxy, C₁₋₄ alkoxyethoxy or benzyloxy,

R_(2a) is hydrogen, chloro, bromo, C₁₋₂ alkyl, C₁₋₄ alkoxy, phenyl-(C₁₋₃ alkoxy), acyloxy or acylamino,

R_(3a) and R_(4a) independently are selected from hydrogen, C₁₋₁₂ alkyl, C₃₋₄ alkenyl, C₃₋₄ alkynyl, benzyl and C₂₋₆ alkyl substituted by 1 or 2 substituents independently selected from hydroxy, C₁₋₄ alkoxy, acyloxy, chloro, bromo, cyano, phenyl, phenoxy and C₁₋₃ alkoxycarbonyl, and

Aa is C₃₋₇ alkylene or a group of the formula --O--C₂₋₄ alkylene-, with the proviso that the N-atom of the group of formula IIIa is not attached to the oxygen atom.

Preferably, R_(1a), when C₁₋₄ alkoxyethoxy, is 2-(C₁₋₄ alkoxy)ethoxy.

Preferably R_(1a) is R_(1a) ' where R_(1a) ' is hydrogen or C₁₋₂ alkoxy.

Preferably R_(2a) is R_(2a) ' where R_(2a) ' is hydrogen, methyl, C₁₋₂ alkoxy, C₁₋₂ -alkyl)carbonylamino or (C₁₋₂ (alkoxy)-carbonylamino.

Preferably each of R_(3a) and R_(4a) independently is selected from hydrogen, C₁₋₈ alkyl, C₃₋₄ alkenyl and C₂₋₆ alkyl substituted by one substituent selected from --OH, (C₁₋₂ -alkyl)carbonyloxy, C₁₋₂ -alkoxycarbonyloxy, cyano and (C₁₋₃ alkoxy)carbonyl, the unsaturation of the C₃₋₄ alkenyl group and the substituent of the substituted alkyl group preferably being in other than the 1-position.

In formulae IIa and IIIa:

Preferred acyloxy groups are selected from --O--CO--R_(5a), --O--CO--OR_(5a), --O--CO--NR₆ R₇, --O--SO₂ --R_(5a) and --O--SO₂ --NR₆ R₇ and preferred acylamino groups are selected from --NH--CO--R_(5a), --NH--CO--OR_(5a), --NH--CO--NH₂, --NH--CO--NHR_(5a), --NH--CO--NR₆ R₇, --NH--SO₂ R_(5a) and --NH--SO₂ --NR₆ R₇, in which

each R_(5a) independently is selected from linear or branched C₁₋₆ alkyl, unsubstituted or substituted by one group selected from chloro, bromo, --OH, C₁₋₃ alkoxy and phenoxy; C₅₋₆ cycloalkyl; C₃₋₄ -alkenyl, unsubstituted or substituted by chloro or bromo; phenyl, unsubstituted or substituted by 1 to 3 substituents independently selected from chloro, bromo, C₁₋₂ alkyl and C₁₋₂ alkoxy; and methyl or ethyl substituted by a phenyl group, and

R₆ and R₇ are as defined above.

When A or Aa is C₃₋₇ alkylene, there are preferably at least three carbon atoms between the nitrogen atom and the benzene ring and when A or Aa is --O--C₂₋₄ alkylene-, there are preferably at least two carbon atoms between the oxygen and nitrogen atoms.

Preferably, any substituted alkyl group as a significance of R₃, R_(3a), R₄ and R_(4a) is monosubstituted.

Preferably, the unsaturation of any C₃₋₄ alkenyl or alkynyl group as a significance of R₃, R_(3a), R₄ or R_(4a) is in other than the 1-position.

Preferred compounds of formula I are of formulae Ia, Ib, Ic and Id: ##STR5## where R₈ is --CH═CH₂, --CH═CH--CH₃, C₁₋₆ alkyl, --CH₂ Cl, --CH₂ CH₂ Cl or --CH₂ OC₆ H₅, and

R₉ is C₁₋₆ alkyl or --(CH₂)_(n) --A₁ --C₁₋₆ alkyl, ##STR6## where R₁₀ is --CH₃, --C₂ H₅, or --(CH₂)_(n) --A₁ --C₁₋₆ alkyl (e.g., --C₂ H₄ --O--CH₃ and --C₂ H₄ --O--C₂ H₅), ##STR7## where R₁₁ is hydrogen, --CH₃, --C₂ H₅ or --NHCOR₈,

each

R₁₂ independently is C₁₋₄ alkyl or --(CH₂)₂₋₆ --O--C₆ H₅, with

the proviso that at most one R₁₂ is --(CH₂)₂₋₆ --O--C₆ H₅, ##STR8## where each of the symbols not defined in connection with a formula is as defined above. In formulae Ia-Id, n is preferably n'.

The compounds of formula I may be prepared by coupling a diazotised amine of formula IV ##STR9## with a compound of formula V

    H--K                                                       (V)

where

K is defined above.

Alternatively, the compounds of formula I may be prepared by reacting a compound of formula VI ##STR10## where X is halogen, preferably chloro or bromo, and K is defined above, with a salt of thiocyanic acid.

The compound of formula IV is known and the compounds of formulae V and VI may be made from known compounds according to known procedures. Diazotisation and coupling can be carried out according to known methods.

The reaction of a compound of formula VI with a salt of thiocyanic acid (preferably an alkali metal or ammonium salt) is usually carried out in the presence of an aprotic solvent, for example dimethylformamide, N-methylpyrrolidone, sulpholane or dimethylsulphoxide, and the reaction takes place easily. Other solvents may be used, for example an alcohol or a mixture of water and organic solvent. Phase transfer conditions may be used.

Dyeing preparations of the compounds of formula I may be formulated by known methods, for example by grinding in the presence of a dispersing agent or a filling material. The preparation (which may be vacuum dried or atomised dried) can be used for dyeing, padding or printing with the addition of water in a short or long dyebath.

The dyestuffs exhaust very well from aqueous suspension on textile material of semi-synthetic or fully synthetic hydrophobic high molecular weight material. The dyestuffs exhaust particularly well on textile material formed from linear aromatic polyester or cellulose 21/2-acetate, cellulose triacetate or synthetic polyamides.

The resulting dyeings show overall good fastnesses, in particular good light fastness, wet fastness (for example washing and sweat fastness) and sublimation fastness. The dyestuffs also produce a large colouring strength and excellent brilliance.

The invention will now be illustrated by the following Examples in which all parts and percentages are by weight and all temperatures are in °C.

EXAMPLE 1

10 Parts of 2,4-dinitro-5-thiocyanoaniline in 120 parts of an 85% orthophosphoric acid solution are reacted at -10° with 13.5 parts of a 40% solution of nitrosylsulphuric acid in concentrated sulphuric acid. The mixture is stirred for 6 hours at this temperature and then a mixture of 6.3 parts of N,N-diethyl-m-toluidine, 70 parts of hydrochloric acid and 70 parts of ice is slowly added to the resulting suspension. After addition the reaction mass is warmed to 10° and stirred for 16 hours. The dyestuff of formula X ##STR11##

results and is filtered, washed in water and vacuum dried. The resulting dyestuff is of a blue colour.

EXAMPLE 2

The dyestuff of formula XI ##STR12##

is prepared by diazotising 5-chloro-2,4-dinitroaniline and coupling with N,N-diethyl-m-toluidine in an analogous manner to that of Example 1. 10 Parts of the above dyestuff XI are stirred with 2.5 parts of potassium thiocyanate in 100 parts of dimethylformamide for 16 hours at 80° C. The reaction mixture is cooled to room temperature and 1500 parts of water are added. The product that results is the dyestuff of formula X defined in Example 1. The product is filtered, washed with water and vacuum dried and has a blue shade.

EXAMPLES 3 TO 90

Compounds of formula XII ##STR13##

in which R₁ to R₄ are defined in Table I below, can be prepared by a method analogous to Example 1 or Example 2. The shades of the dyes produced is given in Table 1. PES is polyester.

                                      TABLE 1                                      __________________________________________________________________________     EX.                                                       Shade                No.                                                                               R.sub.1    R.sub.2         R.sub.3     R.sub.4         on                   __________________________________________________________________________                                                               PES                   3 H          H               C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5 blue                  4 CH.sub.3   H               "           "               "                     5 C.sub.2 H.sub.5                                                                           H               "           "               "                     6 OCH.sub.3  NHCOCH.sub.3    CH.sub.2 CH.sub.2 OCOCH.sub.3                                                              CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  green                 7 OC.sub.2 H.sub.5                                                                          "               "           "               "                     8 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                       "               "           "               "                     9 OCH.sub.2 C.sub.6 H.sub.5                                                                 "               "           "               "                    10 H          C.sub.2 H.sub.5 C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5 "                    11 H          Cl              CH.sub.3    CH.sub.3        violet               12 H          Br              "           "               "                    13 H          OCH.sub. 3      C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5 blue                 14 H          O(CH.sub.2).sub.3 CH.sub.3                                                                     "           "               "                    15 H          OCH.sub.2 C.sub.6 H.sub.5                                                                      "           "               "                    16 H          O(CH.sub.2).sub.3 C.sub.6 H.sub.5                                                              "           "               "                    17 H          OCOCH.sub.3     "           "               "                    18 H          OCOC.sub.6 H.sub.5                                                                             "           "               "                    19 H          OCOOC.sub.2 H.sub.5                                                                            "           "               "                    20 H          OCON(CH.sub.3).sub.2                                                                           "           "               "                    21 H          OSO.sub.2 CH.sub.3                                                                             "           "               "                    22 H          OSO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                            "           "               "                    23 H                                                                                          ##STR14##      "           "               "                    24 H                                                                                          ##STR15##      "           "               "                    25 H          NHCOCH.sub. 3   "           "               "                    26 H          NHCOC.sub.2 H.sub.5                                                                            "           "               "                    27 H          NHCO(CH.sub.2).sub.5 CH.sub.3                                                                  "           "               "                    28 H          NHCOCH.sub.2 Cl "           "               "                    29 H          NHCOCH.sub.2 Br "           "               "                    30 H          NHCOCH.sub.2 CH.sub.2 Cl                                                                       "           "               "                    31 H          NHCO(CH.sub.2).sub.3 OH                                                                        "           "               "                    32 H          NHCOCH.sub.2CHCH.sub.2                                                                         "           "               "                    33 H                                                                                          ##STR16##      "           "               "                    34 H          NHCOCH.sub.2 OC.sub.6 H.sub.5                                                                  "           "               "                    35 H          NHCOOCH.sub.3   "           "               "                    36 H          NHCOOC.sub.2 H.sub.5                                                                           "           "               "                    37 H          NHCOOCH.sub.2 CH(CH.sub.3).sub.2                                                               "           "               "                    38 H          NHCOOC.sub.6 H.sub.5                                                                           "           "               "                    39 H          NHCOOCH.sub.2 C.sub.6 H.sub.5                                                                  "           "               "                    40 H          NHCOOCH.sub.2CHCH.sub.2                                                                        "           "               "                    41 H          NHCOOCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                        "           "               "                    42 H          NHCONH.sub.2    "           "               "                    43 H          NHCONHCH.sub.3  "           "               "                    44 H          NHCONH(CH.sub.2).sub.3 CH.sub.3                                                                "           "               "                    45 H          NHCONHC.sub.6 H.sub.5                                                                          "           "               "                    46 H          NHCON(C.sub.2 H.sub.5).sub.2                                                                   "           "               "                    47 H          CH.sub.3        "           H               violet               48 H          "               "           CH.sub.3        blue                 49 H          "               "           (CH.sub.2).sub.3 CH.sub.3                                                                      "                    50 H          "               "           CH.sub.2 CH.sub.2 CH(CH.sub.3).s                                               ub.2            "                    51 H          "               "           (CH.sub.2).sub.5 CH.sub.3                                                                      "                    52 H          "               "           (CH.sub.2).sub.9 CH.sub.3                                                                      "                    53 H          "               "           (CH.sub.2).sub.11 CH.sub.3                                                                     "                    54 H          "               "           CH.sub.2 C.sub.6 H.sub.5                                                                       "                    55 H          "               "           CH.sub.2 CH.sub.2 C.sub.6                                                      H.sub.5         blue                 56 H          "               "           (CH.sub.2).sub.3 C.sub.6                                                       H.sub.5         "                    57 H          "               "           CH.sub.2 CH.sub.2 Cl                                                                           violet               58 H          "               "           CH.sub.2 CH.sub.2 CN                                                                           "                    59 H          "               "           CH.sub.2 CH.sub.2 OH                                                                           "                    60 H          "               "           CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  "                    61 H          "               "           CH.sub.2 CH.sub.2 OCOC.sub.6                                                   H.sub.5         "                    62 H          "               "           CH.sub.2 CH.sub.2 OCONHC.sub.6                                                 H.sub.5         "                    63 H          "               "           CH.sub.2 CH.sub.2 OC.sub.2                                                     H.sub.5         "                    64  H         "               "           CH.sub.2 CH.sub.2 OC.sub.6                                                     H.sub.5         "                    65 H          "               "           (CH.sub.2).sub.3 OC.sub.6                                                      H.sub.5         "                    66 H          "               "           (CH.sub.2).sub.4 OC.sub.6                                                      H.sub.5         "                    67 H          "               "           (CH.sub.2).sub.5 OC.sub.6                                                      H.sub.5         "                    68 H          "               "           (CH.sub.2).sub.6 OC.sub.6                                                      H.sub.5         "                    69 H          "               "           CH.sub.2CHCH.sub.2                                                                             "                    70 H          "               "           CH.sub.2CHCHCH.sub.3                                                                           "                    71 H          "               "           CH.sub.2CCH     "                    72 H          "               "           CH.sub.2 CH.sub.2COOC.sub.2                                                    H.sub.5         "                    73 H          "               "           CH.sub.2 CH(OH)CH.sub.2                                                        OC.sub.6 H.sub.5                                                                               "                    74 OCH.sub.3  NHCOCH.sub.3    "           C.sub.2 H.sub.5 green                75 OC.sub.2 H.sub.5                                                                          "               "           "               "                    76 H          NHCOC.sub.6 H.sub.5                                                                            "           "               blue                 77 H                                                                                          ##STR17##      "           "               "                    78 H          NHCO(CH.sub.2).sub.2 CH.sub.3                                                                  "           "               "                    79 H          NHCOCH(CH.sub.3).sub.2                                                                         "           "               "                    80 H          NHCOCH.sub.2 CH(CH.sub.3).sub.2                                                                "           "               "                    81 H          NHCO(CH.sub.2).sub.4 CH.sub.3                                                                  "           "               "                    82 H          NHCOC(CH.sub.3).sub.3                                                                          "           "               "                    83 H          CH.sub.3        (CH.sub.2).sub.3 CH.sub.3                                                                  (CH.sub.2).sub.3 CH.sub.3                                                                      "                    84 H          "               CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                       CH.sub.2 CH.sub.2 CH(CH.sub.3).s                                               ub.2            "                    85 H          CH.sub.3        (CH.sub.2).sub.5 CH.sub.3                                                                  (CH.sub.2).sub.5 CH.sub.3                                                                      blue                 86 H          H               C.sub.2 H.sub.5                                                                            CH.sub.2 CH.sub.2OC.sub.6                                                      H.sub.5         violet               87 H          H               CH.sub.2 CH.sub.2 CN                                                                       CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  red                  88 H          H               CH.sub.2 CH.sub.2 OCOCH.sub.3                                                              "               violet               89 CH.sub.3   CH.sub.3        H           (CH.sub.2).sub.5 CH.sub.3                                                                      "                    90 OCH.sub.3  CH.sub.3        CH.sub.3                                                                                    ##STR18##      greenish-            __________________________________________________________________________                                                               blue            

EXAMPLES 91 TO 96

Compounds of formula XIII ##STR19##

in which R₂ to R₄ and A are defined in Table 2 below, can be prepared by a method analogous to that of Example 1 or 2. The shade of the dye produced is given in Table 2.

                  TABLE 2                                                          ______________________________________                                                                                Shade                                   EX.                                    on                                      No.  R.sub.2 R.sub.4    A              PES                                     ______________________________________                                         91   --H     --(CH.sub.2).sub.5 CH.sub.3                                                               --(CH.sub.2).sub.3 --                                                                         blue                                    92   --H       "        --CH(CH.sub.3)CH.sub.2 C(CH.sub.3).sub.2 --                                                   "                                       93   --H     --H          "            "                                       94   --CH.sub.3                                                                             --H          "            "                                       95   --CH.sub.3                                                                             --(CH.sub.2).sub.5 CH.sub.3                                                                 "            "                                       96   --H       "        --O--CH.sub.2 --CH(CH.sub.3)--                                                                "                                       ______________________________________                                    

EXAMPLES 97 TO 105

Compounds of the formula ##STR20## can be prepared by a method analogous to that of Example 1 from known compounds.

    ______________________________________                                         Example                                                                        No.    R.sub.3       R.sub.4    R.sub.5                                        ______________________________________                                          97    --C.sub.2 H.sub.5                                                                            --C.sub.2 H.sub.5                                                                         --CH═CH.sub.2                               98    --(CH.sub.2).sub.3 CH.sub.3                                                                    "          "                                             99    --(CH.sub.2).sub.2 CH(CH.sub.3).sub.2                                                          "          "                                            100    --(CH.sub.2).sub.2 CH.sub.3                                                                  --(CH.sub.2).sub.2 CH.sub.3                                                                 "                                            101    --(CH.sub.2).sub.3 CH.sub.3                                                                    "          "                                            102    --(CH.sub.2).sub.2 CH(CH.sub.3).sub.2                                                          "          "                                            103    --(CH.sub.2).sub.5 CH.sub.3                                                                    "          "                                            104    --(CH.sub.2).sub.3 CH.sub.3                                                                  --(CH.sub.2).sub.3 CH.sub.3                                                                 "                                            105    --C.sub.2 H.sub.5                                                                            --C.sub.2 H.sub.5                                                                         --CH═CH--CH.sub.3                          ______________________________________                                    

The compounds of Examples 97 to 105 produce blue dyeings on PES.

DYEING EXAMPLE

7 Parts of the dyestuff of Example 1 are ground with 13 parts of sodium ligninsulphonate 25 parts of water and 100 parts of siliquarzite pearls until the average dyestuff particle size is less than 1μ. The suspension so formed is filtered from the siliquarzite pearls and is dried under mild conditions and atomised. 1 Part of the dyestuff preparation so formed is warmed to 60° in 4000 parts of water buffered at pH 5 with monosodium phosphate and disodium phosphate to form a dyebath. 100 Parts of a polyester web is dyed with the dyebath for 1 hour at 130° l C. under pressure. After cooling, rinsing, soaping and a further rinsing, the web is dried. A dyeing is produced having a level blue colour with high fastness properties.

Instead of using the dyestuff of Example 1, any one of the dyestuffs of Examples 2 to 105 can be used in the dyeing method above. 

What is claimed is:
 1. A compound of the formula ##STR21## wherein K₁ is ##STR22## wherein A is C₃₋₇ alkylene or --O--C₂₋₄ alkylene, with the proviso that the oxygen atom of the --O--C₂₋₄ alkylene-radical is attached to the asterisked atom,R₁ is hydrogen, chloro, bromo, C₁₋₄ -alkyl, C₁₋₄ alkoxy, benzyloxy or --O--(CH₂)_(n) --A₁ --C₁₋₆ alkyl,wherein A₁ is --O--, --O--CO--, --O--CO--O-- or --CO--O--, and n is 1, 2, 3, 4, 5 or 6 R₂ is hydrogen, chloro, bromo, C₁₋₂ alkyl, C₁₋₄ alkoxy, phenyl(C₁₋₃ alkoxy), acyloxy or acylamino, and each of R₃ and R₄ is independently hydrogen; C₁₋₁₂ alkyl; C₃₋₄ alkenyl; C₃₋₄ alkynyl; benzyl; C₂₋₆ alkyl substituted by 1 or 2 substituents each of which is independently hydroxy, C₁₋₄ alkoxy, acyloxy, chloro, bromo, cyano, phenyl or phenoxy; or --(CH₂)_(n) --A₁ --C₁₋₆ alkyl, whereinA₁ and n are as defined above, with the proviso that any --(CH₂)_(n) --A₁ --C₁₋₆ alkyl as R₃ or R₄ is other than --(CH₂)_(m) --O--C₁₋₄ -alkyl, --(CH₂)_(m) --O--CO--C₁₋₆ alkyl and --(CH₂)_(m) --O--CO--O--C₁₋₆ alkyl, whereinm is 2, 3, 4, 5 or
 6. 2. A compound of the formula ##STR23## wherein K₁ is ##STR24## wherein A is C₃₋₇ alkylene or --O--C₂₋₄ alkylene, with the proviso that the oxygen atom of the --O--C₂₋₄ alkylene-radical is attached to the asterisked atom,R₁ is hydrogen, chloro, bromo, C₁₋₄ alkyl, C₁₋₄ alkoxy, benzyloxy or --O--(CH₂)_(n) --A₁ --C₁₋₆ alkyl, whereinA₁ is --O--, --O--CO--, --O--CO--O-- or --CO--O--, and n is 1, 2, 3, 4, 5 or 6, R₂ is hydrogen, chloro, bromo, C₁₋₂ alkyl, C₁₋₄ alkoxy, phenyl(C₁₋₃ alkoxy), acyloxy or acylamino, and each of R₃ and R₄ is independently hydrogen; C₁₋₁₂ alkyl; C₃₋₄ alkenyl; C₃₋₄ alkynyl; benzyl; C₂₋₆ alkyl substituted by 1 or 2 substituents each of which is independently hydroxy, C₁₋₄ alkoxy, acyloxy, chloro, bromo, cyano, phenyl or phenoxy; or --(CH₂)_(n) --A₁ --C₁₋₆ alkyl, whereinA₁ and n are as defined above, with the proviso that any --(CH₂)_(n) --A₁ --C₁₋₆ alkyl as R₃ or R₄ is other than --(CH₂)_(m) --O--C₁₋₄ alkyl, --(CH₂)_(m) --O--CO--C₁₋₆ alkyl and --(CH₂)_(m) --O--CO--O--C₁₋₆ alkyl, whereinm is 2, 3, 4, 5 or 6,wherein each acylamino is independently --NH--CO--R₅, --NH--CO--OR₅, --NH--CO--NH₂, --NH--CO--NHR₅, --NH--CO--NR₆ R₇, --NH--SO₂ R₅, --NH--SO₂ --NR₆ R₇ or --NH--CO--(CH₂)_(n) --A₁ --C₁₋₆ alkyl, wherein A₁ is --O--, --O--CO--, --O--CO--O-- or --CO--O--, with the proviso that when A₁ is --O--, the C₁₋₆ alkyl group attached thereto is a C₄₋₆ alkyl group, R₅ is C₁₋₆ alkyl; C₁₋₆ alkyl monosubstituted by chloro, bromo, hydroxy, C₁₋₃ alkoxy or phenoxy; C₅₋₆ cycloalkyl; C₂₋₄ alkenyl; C₂₋₄ alkenyl substituted by chloro or bromo; phenyl; phenyl substituted by 1 to 3 substituents each of which is independently chloro, bromo, C₁₋₂ alkyl or C₁₋₂ alkoxy; or C₁₋₂ alkyl substituted by phenyl, each of R₆ and R₇ is independently C₁₋₄ alkyl; C₁₋₄ alkyl monosubstituted by chloro, bromo, hydroxy or C₁₋₃ alkoxy; phenyl or phenyl substituted by 1 to 3 substituents each of which is independently chloro, bromo, C₁₋₂ alkyl or C₁₋₂ alkoxy or R₆ and R₇ taken together and with the nitrogen atom to which they are attached are pyrrolidino, piperidino or morpholino, and n is 1, 2, 3, 4, 5 or 6, andeach acyloxy is independently --O--CO--R₅, --O--CO--OR₅, --O--CO--NR₆ R₇, --O--SO₂ --R₅ or --O--SO₂ --NR₆ R₇, wherein R₅, R₆ and R₇ are as defined above.
 3. A compound according to claim 2wherein when A is C₃₋₇ alkylene there are at least three carbon atoms between the asterisked atom and the nitrogen atom to which A is attached, and when A is --O--C₂₋₄ alkylene- there are at least two carbon atoms between the oxygen atom of A and the nitrogen to which A is attached, any hydroxy, alkoxy, acyloxy, cyano, phenoxy or alkoxycarbonyl as a substituent on an alkyl group attached to an oxygen or nitrogen atom is in other than the 1-position of the alkyl group, and no carbon atom of a substituted alkyl group has more than one substituent selected from hydroxy, alkoxy, acyloxy, cyano, phenoxy and alkoxycarbonyl, the double bond of any C₃₋₄ alkenyl group as R₃ or R₄ and the triple bond of any C₃₋₄ alkynyl group as R₃ or R₄ are in other than the 1-position, and each n is independently 2, 3 or
 4. 4. A compound according to claim 2wherein R₁ is hydrogen, C₁₋₂ alkoxy or 2-(C₁₋₂ alkoxy)ethoxy, R₂ is hydrogen, methyl, C₁₋₂ alkoxy, (C₁₋₆ alkyl)carbonylamino, (C₁₋₄ alkoxy)carbonylamino, 3-chloropropionamido, vinylcarbonylamino, prop-1-en-1-ylcarbonylamino or --NH--CO--(CH₂)_(n) --A₁ --C₁₋₆ alkyl, whereinA₁ is --O--, --O--CO--, --O--CO--O-- or --CO--O--, and n is 1, 2, 3, 4, 5 or 6, and each of R₃ and R₄ is independently hydrogen, C₁₋₁₂ alkyl, C₃₋₄ alkenyl, C₂₋₆ alkyl monosubstituted by hydroxy, phenoxy, cyano or C₁₋₃ alkoxy; or --(CH₂)_(n') --A₁ --C₁₋₆ alkyl, whereinA₁ is --O--, --O--CO--, --O--CO--O-- or --CO--O--, and n' is 2, 3 or 4, with the proviso that any --(CH₂)_(n') --A₁ --C₁₋₆ alkyl as R₃ or R₄ is other than --(CH₂)_(n') --O--C₁₋₃ alkyl.
 5. A compound according to claim 4wherein R₁ is hydrogen, R₃ is C₁₋₆ alkyl or primary or secondary C₂₋₆ alkyl substituted by phenoxy in other than the 1-position, and R₄ is C₁₋₆ alkyl.
 6. A compound according to claim 2 having the formula ##STR25## wherein R₈ is vinyl, prop-1-en-1-yl, C₁₋₆ alkyl,chloromethyl, 2-chloroethyl or phenoxymethyl, and each R₉ is independently C₁₋₆ alkyl or --(CH₂)_(n) --A₁ --C₁₋₆ alkyl, whereinA₁ is --O--, --O--CO--, --O--CO--O-- or --CO--O--, and n is 1, 2, 3, 4, 5 or
 6. 7. A compound according to claim 6 wherein n is 2, 3 or
 4. 8. A compound according to claim 7 wherein the two R₉ 's are identical.
 9. The compound according to claim 8wherein R₈ is vinyl, and each R₉ is ethyl.
 10. A compound according to claim 2 having the formula ##STR26## wherein R₈ is vinyl, prop-1-en-1-yl, C₁₋₆ alkyl, chloromethyl, 2-chloroethyl or phenoxymethyl, eachR₉ is independently C₁₋₆ alkyl or --(CH₂)_(n) --A₁ --C₁₋₆ alkyl, whereinA₁ is --O--, --O--CO--, --O--CO--O-- or --CO--O--, and n is 1, 2, 3, 4, 5 or 6, and R₁₀ is methyl, ethyl or --(CH₂)_(n) --A₁ --C₁₋₆ alkyl, wherein A₁ and n are as defined above.
 11. A compound according to claim 10 wherein n is 2, 3 or
 4. 12. A compound according to claim 11 wherein the two R₉ 's are identical.
 13. A compound according to claim 2 having the formula ##STR27## wherein R₁₁ is hydrogen, methyl, ethyl or --NH--CO--R₈,whereinR₈ is vinyl, prop-1-en-1-yl, C₁₋₆ alkyl, chloromethyl, 2-chloroethyl or phenoxymethyl, and each R₁₂ is independently C₁₋₄ alkyl or --(CH₂)_(m) --O--C₆ H₅, whereinm is 2, 3, 4, 5 or 6, with the proviso that not more than one R₁₂ is --(CH₂)_(m) --O--C₆ H₅.
 14. The compound according to claim 13 having the formula ##STR28##
 15. A compound according to claim 2 having the formula ##STR29## wherein each R₉ is independently C₁₋₆ alkyl or--(CH₂)_(n) --A₁ --C₁₋₆ alkyl, whereinA₁ is --O--, --O--CO--, --O--CO--O-- or --CO--O--, and n is 1, 2, 3, 4, 5 or 6, and R₁₀ is methyl, ethyl or --(CH₂)_(n) --A₁ --C₁₋₆ alkyl,wherein A₁ and n are as defined above.
 16. A compound according to claim 15 wherein n is 2, 3 or
 4. 17. A compound according to claim 16 wherein the two R₉ 's are identical.
 18. A compound according to claim 15 wherein the two R₉ 's are identical. 